A One-Step Synthesis of 1,4-Bis(1-phospholano)butane

Novel synthetic route for (parent) phosphetanes, phospholanes, phosphinanes and phosphepanes

“…Generally speaking, special reaction conditions such as liquid ammonia as solvent, 12 dilution conditions, slow fractional distillation over long columns for work-up or tedious multi-step syntheses are necessary. 5,11,13 This is accompanied by a lack of selectivity and low yields. In addition, sterically demanding substituents such as tert -butyl groups in the carbon backbone or phenyl groups attached to the phosphorus atom in the starting materials are necessary to stabilise the phosphorus-containing heterocycles by these approaches, which makes access to the corresponding parent (P–H) compounds even more difficult.…”

Ligand Stereoelectronic Effects in Complexes of Phospholanes, Phosphinanes, and Phosphepanes and Their Implications for Hydroformylation Catalysis

“…The phosphacycles L a 5 , 6 were first synthesized over 90 years ago by the reaction of the corresponding BrMgCH 2 (CH 2 ) n CH 2 MgBr ( n = 2, 3) with PhPCl 2 , and more recently all three L a 5 - 7 compounds have been made by intramolecular ring closure reactions of PhP(H)(CH 2 ) n CHCH 2 ( n = 2−4). The NMR spectroscopic properties of L a 5 - 7 have been extensively discussed, but their coordination chemistry has been little studied. ,, The tert -butylphosphacycles L b 5 , 6 have been previously made by substitution reactions of Bu t PCl 2 or Bu t P(OMe) 2 , but the seven-membered 1- ter t-butylphosphepane ( L b 7 ) is new. Rhodium complexes of L b 5,6 have been shown to catalyze the production of ethylene glycol from CO/H 2 mixtures .…”

Synthesis of New Bidentate Phosphine Ligands Containing Saturated Phosphorus Heterocycles

“…The incorporation of saturated phosphorus heterocyclic groups into polydentate phosphine ligand systems has been explored far less. Recently, Brunner and Burk , reported multistep syntheses of chiral bidentate phospholane compounds, and subsequently, Emrich reported a one-step synthesis of the simpler 1,4-bis(1-phospholano)butane. To our knowledge, no simple bidentate phospholanoethanes have yet been reported.…”